JP2005029766A

JP2005029766A - Functional acrylic polymer particle with fixed form and use of the same

Info

Publication number: JP2005029766A
Application number: JP2003273779A
Authority: JP
Inventors: Takehide Misawa; 毅秀三澤; Yosuke Nakada; 洋輔中田
Original assignee: Soken Kagaku KK; Soken Chemical and Engineering Co Ltd
Current assignee: Soken Kagaku KK; Soken Chemical and Engineering Co Ltd
Priority date: 2003-07-11
Filing date: 2003-07-11
Publication date: 2005-02-03
Anticipated expiration: 2023-07-11
Also published as: JP4517083B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide functional polymer particles with a fixed form, associated with various functional polymer particles with the fixed form such as a medical material e.g. a diagnostic agent, coating, ink, electronic materials, PLD, electrostatic toner of a copying machine, etc., and excellent in functions and characteristics such as electrophoretic property, electrically charging property, coloring property, carrying property, etc. <P>SOLUTION: The functional acrylic polymer particles having the fixed form having functional groups localized on the surface of the particles are provided by having at least one functional group in its molecule per 100 pts. mass (meth)acrylic monomer A of the particles, consisting of a copolymer obtained by polymerizing a polymerizable monomer B rich in hydrophobicity in 1-90 pts. mass range, and localizing at least ≥70 % total amount of the functional groups in the particles with the fixed form based on mass % so as to stick their heads out of the surface of the particles. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、機能性ポリマー定形粒子に関し、より詳細には、電気泳動性、帯電性、着色性、担持性、反応性等に代表される特性、機能を発揮させる球状粒子等である機能性ポリマー定形粒子及びその用途に関する。 TECHNICAL FIELD The present invention relates to functional polymer shaped particles, and more specifically, a functional polymer that is a spherical particle or the like that exhibits characteristics and functions typified by electrophoretic properties, chargeability, colorability, supportability, and reactivity. It relates to shaped particles and their uses.

従来から、粒子形状の定形、不定形を問わず多種多様の機能を発揮する機能性有機ポリマー粒子が知られている。その多くは、その重合体ポリマー粒子の粒子表面又は粒子内部に存在する官能基に係わって発揮される機能である。例えば、電子写真画像形成用のトナー、インクジェットプリンター用インク、印刷用水性インク、筆記用水性インク、スタンプ用インク、コーティング剤、水性塗料、化粧品等に着色性、着色材としての機能性着色樹脂微粒子が広く用いられている。また、このような着色微粒子は、診断薬用担体としても使用されている。また、各種の電子部品や、光調光材等に用いられるカラーフィルタのような着色層の薄膜化のためにも用いられている。 Conventionally, functional organic polymer particles that exhibit a wide variety of functions regardless of whether the particle shape is regular or irregular are known. Most of them are functions exerted in relation to functional groups present on the surface or inside of the polymer polymer particles. For example, toner for electrophotographic image formation, ink for inkjet printer, water-based ink for printing, water-based ink for writing, ink for stamping, coating agent, water-based paint, cosmetics, etc. Is widely used. Such colored fine particles are also used as a carrier for diagnostic agents. Moreover, it is used also for thinning of a colored layer like a color filter used for various electronic parts, a light control material, etc.

すなわち、［特許文献１］には、ヒドラジン架橋による架橋ポリ（メタ）アクリロニトリル系重合体粒子の残存ニトリル基の０．１％以上がイオン交換又はイオン配位可能なカルボキシル基等の極性基に変換されている架橋ポリマー粒子が記載されている。また、イオン交換法で極性基に金属イオンを担持させた後、還元処理させて担持金属イオンを金属微粒子化させてなる金属微粒子を含有するポリマー粒子が記載されている。 That is, in [Patent Document 1], 0.1% or more of the remaining nitrile groups of the crosslinked poly (meth) acrylonitrile polymer particles by hydrazine crosslinking are converted into polar groups such as carboxyl groups capable of ion exchange or ion coordination. Crosslinked polymer particles are described. Further, there is described a polymer particle containing metal fine particles obtained by supporting metal ions on a polar group by an ion exchange method and then reducing the metal ions into metal fine particles by reduction treatment.

また、［特許文献２］には、水溶性塩基性染料が溶解するカルボキシル基等の極性基を有する水溶解度が１０％以下のビニルモノマーと、ＭＭＡ等のアクリル系の疎水性ビニルモノマーとを乳化重合させてなる重合反応染色法によって染料着色された水性インク用着色樹脂微粒子が記載されている。 [Patent Document 2] emulsifies a vinyl monomer having a polar group such as a carboxyl group in which a water-soluble basic dye is dissolved and having a water solubility of 10% or less and an acrylic hydrophobic vinyl monomer such as MMA. Colored resin fine particles for water-based inks dyed by a polymerization reaction dyeing method obtained by polymerization are described.

そこで、近年に至って、着色樹脂微粒子であって、電気泳動表示セル内で電気的に帯電して、泳動させる帯電性着色樹脂微粒子に係わって、電気泳動表示装置が提案されている。例えば、［特許文献３］には、単純マトリックス駆動による表示コントラストを可能にさせる電気泳動表示装置が提案され、シリコーンオイル、トルエン、キシレン、高純度石油等の透明有機絶縁液体セルに装填される着色帯電泳動微粒子として黒、白又はＲＧＢに係わる着色粒子が記載されている。また、このような泳動粒子として、絶縁性液体中で帯電特性を発揮するポリエチレン、ポリスチレン等の平均粒子径０．５〜２０μｍの樹脂粒子が開示されている。 Therefore, in recent years, an electrophoretic display device has been proposed in connection with charged colored resin fine particles that are colored resin fine particles and are electrically charged and electrophoresed in an electrophoretic display cell. For example, [Patent Document 3] proposes an electrophoretic display device that enables display contrast by simple matrix drive, and is loaded into a transparent organic insulating liquid cell such as silicone oil, toluene, xylene, high-purity petroleum, or the like. Colored particles relating to black, white or RGB are described as the charged electrophoretic fine particles. Further, as such migrating particles, resin particles having an average particle diameter of 0.5 to 20 μm, such as polyethylene and polystyrene, which exhibit charging characteristics in an insulating liquid are disclosed.

また、［特許文献４］には、静電荷像現像用トナー粒子として粒子径が６〜８μｍのスチレンとメチルアクリレート、ｎ−ブチルメタアクリレート、２−エチルヘキシルメタクリレート等とのスチレン−（メタ）アクリル系共重合体の青色、黄色、赤色等の染料含有着色樹脂粒子が記載され、ブローオフ法によるその帯電量が、−２５〜−３０（μクーロン／ｇ）範囲の帯電特性を発揮する樹脂粒子として提案されている。その調製方法としては、着色剤の染料をアルコール系溶媒に溶かした系に、シード重合法や懸濁重合法で重合成長させて得られた熱可塑性の樹脂粒子を添加させて、重合反応染色法で染料を染着させるものである。 [Patent Document 4] describes a styrene- (meth) acrylic system of styrene having a particle size of 6 to 8 μm and methyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like as toner particles for developing an electrostatic charge image. Copolymer blue, yellow and red dye-containing colored resin particles are described, and the charge amount by blow-off method is proposed as resin particles exhibiting charging characteristics in the range of −25 to −30 (μ coulomb / g). Has been. As a preparation method, a thermoplastic resin particle obtained by polymerizing and growing by a seed polymerization method or a suspension polymerization method is added to a system in which a colorant dye is dissolved in an alcohol solvent, and then a polymerization reaction dyeing method is used. In order to dye the dye.

また、このような着色樹脂微粒子に係わって、［特許文献５］には、油溶性染料を含有させた平均粒子径０．５〜１００μｍのアクリル系着色樹脂微粒子が記載され、例えば、（メタ）アクリル系モノマーとスチレン系モノマーとの共重合体からなる着色樹脂微粒子が開示されている。その調製方法として、水系媒体中に分散する乳化重合又は懸濁重合等によって調製された平均粒子径が０．０５〜１μｍのシード粒子に、アクリル系モノマーと油溶性染料とを吸収させて反応重合染色法で染料着色させるものである。 Further, in connection with such colored resin fine particles, [Patent Document 5] describes acrylic colored resin fine particles having an average particle diameter of 0.5 to 100 μm containing an oil-soluble dye. Disclosed is a colored resin fine particle comprising a copolymer of an acrylic monomer and a styrene monomer. As a preparation method thereof, an acrylic monomer and an oil-soluble dye are absorbed into seed particles having an average particle diameter of 0.05 to 1 μm prepared by emulsion polymerization or suspension polymerization dispersed in an aqueous medium, and reactive polymerization is performed. The dye is colored by a dyeing method.

また、［特許文献６］には、粒子表面に所望する機能を付与させる機能性基として、カルボキシル基、アミノ基、水酸基等を有する平均粒子径が３０ｎｍ〜２μｍの機能性ポリアミドの単分散球状粒子が記載されている。その用途として、例えば、電子材料、医療用材料（診断薬、ＤＤＳ用材料、蛍光マーカー剤）、フォトニクス材料、クロマクトグラフ用材料等が開示されている [Patent Document 6] describes a monodispersed spherical particle of functional polyamide having an average particle diameter of 30 nm to 2 μm having a carboxyl group, an amino group, a hydroxyl group, etc. as a functional group for imparting a desired function to the particle surface. Is described. As its applications, for example, electronic materials, medical materials (diagnostic agents, DDS materials, fluorescent marker agents), photonics materials, chromatograph materials, and the like are disclosed.

また、［特許文献７］には、筆記用インク、印刷用インク、インクジェット（ＩＪ）記録用インク、塗料及びカラーフィルタ等に用いられる特定単量体を含有する単量体組成物と油溶性染料と有機珪素単量体とを、重合開始剤、反応性乳化剤（又は重合性乳化剤）下及び非反応性乳化剤との併用下に乳化重合させたナノサイズの着色微粒子を含有する着色樹脂エマルジョンが記載され、特に、染料が均一に、高濃度に配合され、且つ耐熱性、耐光性、耐溶剤性、耐水性及び耐剥離性等の耐久性に優れる着色樹脂エマルジョン及びその着色微粒子が提案されている。 [Patent Document 7] discloses a monomer composition and an oil-soluble dye containing specific monomers used for writing ink, printing ink, ink jet (IJ) recording ink, paint, color filter, and the like. A colored resin emulsion containing nano-sized colored fine particles obtained by emulsion polymerization of an organic silicon monomer with a polymerization initiator, a reactive emulsifier (or polymerizable emulsifier) and a non-reactive emulsifier In particular, a colored resin emulsion and colored fine particles thereof, in which a dye is uniformly mixed at a high concentration and excellent in durability such as heat resistance, light resistance, solvent resistance, water resistance, and peel resistance, have been proposed. .

また、［特許文献８］には、油溶性染料で着色されたポリエステル系樹脂、ビニル系樹脂、スチレン系樹脂及びスチレン−アクリル系共重合体等の樹脂が、乳化された水性分散体中に、ナノサイズの着色樹脂微粒子として分散するＩＪ用水性インクが記載されている。すなわち、重合性モノマー中に、油溶性染料を溶解又は分散させて、例えば、ポリエステル系樹脂の重合時に、イオン性基としてカルボン酸アルカリ金属塩を有する単量体を導入させて乳化重合させて、油溶性染料で着色されたポリエステル系樹脂粒子が、アセトン等の水溶性有機溶媒を含有する水性分散体中に、着色微粒子として分散するＩＪ用水性インクである。 In [Patent Document 8], a resin such as a polyester resin, a vinyl resin, a styrene resin, and a styrene-acrylic copolymer colored with an oil-soluble dye is incorporated into an emulsified aqueous dispersion. A water-based ink for IJ dispersed as nano-sized colored resin fine particles is described. That is, an oil-soluble dye is dissolved or dispersed in a polymerizable monomer, for example, when a polyester resin is polymerized, a monomer having a carboxylic acid alkali metal salt as an ionic group is introduced, and emulsion polymerization is performed. This is an IJ aqueous ink in which polyester resin particles colored with an oil-soluble dye are dispersed as colored fine particles in an aqueous dispersion containing a water-soluble organic solvent such as acetone.

特開平０９−１８８７７８号公報JP 09-188778 A 特開平１０−２５９３３７号公報JP-A-10-259337 特開２００１−２４９３６６号公報JP 2001-249366 A 特開平０４−２４３２６７号公報Japanese Patent Laid-Open No. 04-243267 特開２００１−８９５１０号公報JP 2001-89510 A 特開２０００−２４８０６３号公報JP 2000-248063 A 特開２０００−２９７１２６号公報JP 2000-297126 A 特開２０００−２９７２３４号公報JP 2000-297234 A

以上のような状況下にあって、例えば、電気泳動表示セル内に充装する絶縁性の無色透明又は着色透明流体中を、帯電着色樹脂微粒子を電気的に泳動させて画像及び／又は印字表示させるペーパーライクディスプレ（ＰＬＤ）には、電界系で帯電する染顔料で着色されている着色樹脂微粒子なる機能性定形ポリマー粒子が係わっている。また、この着色重合体微粒子がＰＬＤとしての表示形態を可能にさせるには、対向する電極表示セル内での帯電性、電気泳動性が極めて重要である。従って、このＰＬＤに用いる機能性定形ポリマー粒子は、電界系にあって電気的に応答し易い帯電性を呈する着色樹脂粒子である。また、泳動粒子の凝集を防止させて泳動ディスプレ性をスムーズにさせる観点から、粒子形状が定形で、好ましくは球状粒子で、好ましくは、その粒子径の分布度（バラツキ度）の少ない単分散粒子であることが望ましい。更には、複写機、レザープリンター、ファクシミリー等の電子写真画像形成装置には、静電トナーなる帯電性の機能性着色樹脂微粒子が係わっている。このような帯電性着色樹脂微粒子は、前者のセル内の電界系で、泳動時に凝集粗大化を起こし難く、後者の転写・定着系でも凝集し難くい、粒子径の均斉度の高い単分散性の機能性定形粒子が求められる。 Under the circumstances as described above, for example, images and / or print displays are made by electrically moving charged colored resin fine particles in an insulating colorless transparent or colored transparent fluid filled in an electrophoretic display cell. The paper-like display (PLD) to be used is related to functional regular polymer particles, which are colored resin fine particles colored with a dye pigment charged in an electric field system. In addition, in order to enable the colored polymer fine particles to have a display form as a PLD, the chargeability and the electrophoretic properties in the opposing electrode display cells are extremely important. Therefore, the functional regular polymer particles used in the PLD are colored resin particles that are in an electric field system and exhibit chargeability that easily responds electrically. In addition, from the viewpoint of preventing migration particles from agglomerating and smoothing the migration display property, the particle shape is a regular shape, preferably a spherical particle, and preferably a monodisperse particle having a small degree of distribution (variation degree) of the particle size. It is desirable that Furthermore, electrophotographic image forming apparatuses such as copying machines, leather printers, facsimiles, and the like are associated with electrostatically functional functional colored resin fine particles that are electrostatic toners. These charged colored resin fine particles are monodisperse in the former electric field system in the cell, which is less likely to cause aggregation and coarsening during migration, and less likely to aggregate in the latter transfer / fixing system. Functionally shaped particles are required.

そこで、本発明者らは、機能性粒子としての着色性樹脂粒子に係わって、その定形球状粒子に含有する官能基量に着目させて、既に特願２００２−８３８９４で、シード重合による重合反応染色法によって染料着色させ、粒子表面が（＋）又は（−）に帯電する帯電性アクリル系着色樹脂微粒子及びその製造方法を提案している。すなわち、着色剤である油溶性染料及び／又は顔料を溶解及び／又は分散させる（メタ）アクリル系モノマーと、分子内に少なくとも１個以上の官能基を有する重合性モノマーとから、平均粒子径０．１〜２０μｍのシード粒子である球状粒子が分散する水系分散液に、強攪拌下に（メタ）アクリル系モノマーと、分子内に少なくとも１個以上の官能基を有する重合性モノマーと、着色剤の油溶性染料と、乳化剤及び水とを含有させた混合溶液を添加させて、平均粒子径１．０〜３０μｍの範囲にある粒子形状が球状で、単分散粒子の帯電性アクリル系着色球状粒子及びそのシード重合法による製造方法が提案されている。 Therefore, the present inventors have been concerned with coloring resin particles as functional particles, and have focused attention on the amount of functional groups contained in the regular spherical particles. In Japanese Patent Application No. 2002-83894, polymerization reaction dyeing by seed polymerization has already been performed. The present invention proposes a chargeable acrylic colored resin fine particle which is dyed by a method and has a particle surface charged to (+) or (−) and a method for producing the same. That is, an average particle size of 0 is obtained from a (meth) acrylic monomer that dissolves and / or disperses an oil-soluble dye and / or pigment that is a colorant, and a polymerizable monomer having at least one functional group in the molecule. A (meth) acrylic monomer, a polymerizable monomer having at least one functional group in the molecule, and a colorant in an aqueous dispersion in which spherical particles as seed particles of 1 to 20 μm are dispersed under strong stirring A mixed solution containing an oil-soluble dye, an emulsifier and water is added, and the particle shape in the range of an average particle size of 1.0 to 30 μm is spherical, and the monodisperse charged charged acrylic colored spherical particles And the manufacturing method by the seed polymerization method is proposed.

また、本発明者らは、既に特願２００２−０１４９９９で、乳化重合による重合反応着色法によって、より多くの染料を内包及び沈着させて、より高色調の着色樹脂粒子及びその製造方法を提案している。すなわち、乳化重合下に樹脂微粒子を形成させながら、前駆体粒子としてエマルジョン中に油溶性染料を重合体樹脂に内包する平均粒子径１０〜６００ｎｍの親水性着色樹脂粒子を分散させ、更に反応性の二次乳化剤と、油溶性染料と、染料親水化助剤等を添加させ、攪拌・加温下にエマルジョン中に、更に染料を沈着被覆させて染料内包粒子の表層及びその近傍層に染料が沈着被覆させて高色調の約１０〜６００ｎｍ範囲にあるナノサイズの超微細な親水性着色樹脂微粒子及び染料２段階固定化による製造方法が提案されている。 In addition, the present inventors have already proposed, in Japanese Patent Application No. 2002-014999, a colored resin particle having higher color tone and a method for producing the same by encapsulating and depositing more dye by a polymerization reaction coloring method by emulsion polymerization. ing. That is, while forming resin fine particles under emulsion polymerization, hydrophilic colored resin particles having an average particle diameter of 10 to 600 nm in which an oil-soluble dye is encapsulated in the polymer resin as a precursor particle are dispersed. Add secondary emulsifier, oil-soluble dye, dye hydrophilization aid, etc., and stir and heat to add emulsion to the emulsion and deposit the dye on the surface layer of the dye-encapsulated particles and its neighboring layers. A nano-sized ultrafine hydrophilic colored resin fine particle having a high color tone in the range of about 10 to 600 nm and a production method by two-stage fixing of a dye have been proposed.

そこで、本発明の目的は、従来から種々提案されている電気泳動性、帯電性、着色性、担持性等の特性に代表される各種の機能を発揮させる官能基を有するアクリル系の球状等の定形粒子であって、その機能発現に係わる官能基が、粒子中に内在する官能基と、粒子表面に頭出ししている官能基に着目して、その官能基の全量に着目するよりも、従来のポリマー粒子では不可能であった粒子表面に官能基が高濃度で分布し、このような官能基の分布様相に係わって発揮することを特徴とする機能性アクリル系ポリマー定形粒子を提供することである。 Therefore, an object of the present invention is to provide acrylic spheres having functional groups that exhibit various functions represented by various properties such as electrophoretic properties, charging properties, coloring properties, and support properties that have been conventionally proposed. Rather than focusing on the total amount of the functional group, it is a regular particle, focusing on the functional group involved in the functional expression, the functional group present in the particle and the functional group cueing on the particle surface, Provided is a functional acrylic polymer shaped particle characterized in that functional groups are distributed at a high concentration on the particle surface, which is impossible with conventional polymer particles, and is exerted in relation to the distribution aspect of such functional groups. That is.

本発明者らは、上記課題を解決するために鋭意検討し、通常の水性分散系におけるシード重合法において、アクリル系重合性モノマーに共重合させる官能基を有する重合性モノマー種に着目して、官能基種と重合性基と疎水性基とを有する特定モノマー種を選択し、しかも、樹脂粒子の表面に官能基や置換基を有する樹脂粒子を種々重合形成させたところ、その樹脂粒子表面が容易に帯電してスムーズに泳動する重合体粒子を見出し、本発明を完成させるに至った。 The present inventors have intensively studied to solve the above problems, and in the seed polymerization method in a normal aqueous dispersion, paying attention to a polymerizable monomer species having a functional group to be copolymerized with an acrylic polymerizable monomer, When a specific monomer type having a functional group type, a polymerizable group and a hydrophobic group is selected, and the resin particles having various functional groups and substituents are polymerized on the surface of the resin particles, the resin particle surface is The inventors have found polymer particles that are easily charged and migrate smoothly, and have completed the present invention.

そこで、本発明によれば、各種の機能性を発揮させる粒子中に含有する官能基の多くが、粒子表面又は粒子表面を含むその近傍相に、官能基が頭出しするように遍在（又は局在）していることを特徴とする機能性アクリル系ポリマー定形粒子を提供する。 Therefore, according to the present invention, many of the functional groups contained in the particles exhibiting various functionalities are ubiquitous (or so that the functional groups cue up on the particle surface or its neighboring phase including the particle surface (or Provided are functional acrylic polymer shaped particles characterized by being localized.

すなわち、本発明によるこの定形粒子は、（メタ）アクリル系モノマー（Ａ）の１００質量部当たり、分子内に少なくとも１個の官能基を有する疎水性の重合性モノマー（Ｂ）が１〜９０質量部の範囲で共重合させた外観形状が定形のアクリル系ポリマー粒子である。しかも、質量％基準で表してその定形粒子中に含有する官能基全量の少なくとも７０％以上の官能基が定形粒子表面に頭出し状態になるように重合性モノマー（Ｂ）が重合形成されていることが特徴である。 That is, in the regular particles according to the present invention, the hydrophobic polymerizable monomer (B) having at least one functional group in the molecule is 1 to 90 masses per 100 mass parts of the (meth) acrylic monomer (A). These are acrylic polymer particles having a regular appearance shape copolymerized in a range of parts. In addition, the polymerizable monomer (B) is formed by polymerization so that at least 70% or more of the functional groups contained in the regular particles, expressed on the basis of mass%, are found on the surface of the regular particles. It is a feature.

以上から、本発明による機能性アクリル系ポリマー定形粒子は、シード重合法で得られるアクリル系ポリマー定形粒子であって、（メタ）アクリル系モノマー（Ａ）に共重合させる重合性モノマー（Ｂ）は、例えば、下記式（１）に示す分子構造から明らかなように分子内に有する官能基（又は置換基）が、モノマー分子端の疎水性基に位置し、その疎水性基がモノマー分子の一方端に位置する重合性基から離れた部位に位置する特定の分子構造を有する疎水性に富む重合性モノマーであることが特徴である。 From the above, the functional acrylic polymer regular particles according to the present invention are acrylic polymer regular particles obtained by the seed polymerization method, and the polymerizable monomer (B) to be copolymerized with the (meth) acrylic monomer (A) is For example, as is apparent from the molecular structure represented by the following formula (1), the functional group (or substituent) in the molecule is located in the hydrophobic group at the end of the monomer molecule, and the hydrophobic group is one of the monomer molecules. It is characterized by being a polymerizable monomer rich in hydrophobicity having a specific molecular structure located at a site away from the polymerizable group located at the end.

このような分子構造のモノマーを水性乳化系でシード重合させると、重合性モノマー（Ｂ）はシード粒子に向かって疎水基を背に、重合性基を内側に配向するように（メタ）アクリル系モノマー（Ａ）と共重合する傾向を呈する。その結果、このような分子配向の作用効果下に、シード粒子を核にその周りにシェル状に重合体が形成された重合体粒子の表面には、官能基が、恰も頭出し状にあるように局在している。 When a monomer having such a molecular structure is seed-polymerized in an aqueous emulsion system, the polymerizable monomer (B) is (meth) acrylic so that the polymerizable group is oriented inward with the hydrophobic group back to the seed particle. It tends to copolymerize with the monomer (A). As a result, under the effect of such molecular orientation, the functional groups appear to be cue-like on the surface of the polymer particles in which the polymer is formed in a shell shape around the seed particles as a nucleus. Is localized.

このように本発明による重合体粒子の粒子表面には、特定の分子構造を有する重合性モノマー（Ｂ）に係わる所定の官能基が、頭出し状に高い濃度で局在するように形成される。また、このように粒子表面に官能基が明確に局在する事実は、後述する本発明の実施例に記載する参考実験に示す事実から明確に立証されるように、頭出し状にある官能基量が明確に定量されよく符合している。 Thus, on the particle surface of the polymer particle according to the present invention, the predetermined functional group related to the polymerizable monomer (B) having a specific molecular structure is formed so as to be localized at a high concentration in the form of a head. . In addition, the fact that the functional group is clearly localized on the particle surface in this way is clearly demonstrated from the fact shown in the reference experiment described in the examples of the present invention described later, and the functional group in a cue-like shape. The amount is clearly quantified and matches well.

また、この粒子表面に頭出し状に局在する官能基量が、本発明の特徴である共重合させる重合性モノマー（Ｂ）の理論量にほぼ一致していることから、従来のような粒子内部に官能基が内包しているような粒子に比べると、粒子表面に著しく高濃度に局在させられる。しかも、その局在する官能基量が明確に定量されることから、この表面官能基に係わって発揮される表面帯電性、電気泳動性、染料着色性、担持性、表面反応性等の諸特性及び諸機能を定量的且つより効果的に発揮させることができる。 In addition, since the amount of the functional group localized in the form of a cue on the particle surface substantially coincides with the theoretical amount of the polymerizable monomer (B) to be copolymerized, which is a feature of the present invention, the conventional particles Compared with particles in which functional groups are encapsulated, they are localized at a significantly higher concentration on the particle surface. In addition, since the amount of the localized functional group is clearly quantified, various characteristics such as surface chargeability, electrophoretic properties, dye coloring property, supportability, surface reactivity, etc. exhibited by this surface functional group And various functions can be exhibited quantitatively and more effectively.

また、このように官能基が粒子表面に頭出し状に存在している事実から、例えば、粒子を染料着色させるにおいて、従来のように重合反応時に、形成粒子内に染料を抱え込み内包させる染料内包型着色では、分子の大きさ等から粒子内に吸蔵されにくい染料でも、通常の染色法で粒子表面に効果的に染色させることができる。また、官能基が粒子表面に頭出し状態にある官能基を介して化学的にも表面活性が高い粒子であることから、染料以外の他の化合物、例えば、タンパク質、また、各種の薬価成分等を錯イオン反応又は化学吸着又はイオン交換吸着させられ、各種の機能が粒子表面に効果的に付与させることができる。 In addition, due to the fact that the functional groups are present on the surface of the particles in this way, for example, in the case of coloring the particles with the dye, the dye inclusion in which the dye is held in the formed particles during the polymerization reaction as in the prior art. In mold coloring, even a dye that is not easily occluded in the particle due to the size of the molecule can be effectively dyed on the particle surface by an ordinary dyeing method. In addition, since the functional group is a particle having a high surface activity chemically through a functional group in a cueing state on the particle surface, other compounds other than dyes, such as proteins, various drug price components, etc. Can be effectively imparted to the particle surface by various functions.

以下に、このような本発明による機能性アクリル系ポリマー定形粒子及びその粒子の用途に係わる実施するための最良の形態について更に説明する。 Hereinafter, the functional acrylic polymer regular particles according to the present invention and the best mode for carrying out the application of the particles will be further described.

そこで、既に上述した如く、本発明による機能性アクリル系ポリマー定形粒子は、各種の機能性を発揮させる粒子中に含有する官能基の大部分が、質量％基準で表してその定形粒子中に含有する官能基全量の少なくとも７０％以上で、好ましくは９０％以上で、更に好ましくは、ほぼ１００％が粒子表面又は粒子表面を含むその近傍層に、官能基が明確に頭出しするように局在（又は偏在）している。すなわち、本発明によるこのような機能性定形粒子は、水性乳化系におけるシード粒子を核にして、（メタ）アクリル系モノマー（Ａ）に、乳化重合下に共重合させて、シード粒子を粒成長させる共重合性モノマー（Ｂ）は、分子内に重合性基と少なくとも１個の官能基を有し、しかも、その官能基が疎水性基に結合され、好ましくは、その疎水性基がモノマー分子の分子端に位置している疎水性に富む重合性モノマー（Ｂ）なる特定分子構造を有するモノマーであることが好適である。 Therefore, as already mentioned above, the functional acrylic polymer regular particles according to the present invention contain most of the functional groups contained in the particles exhibiting various functionalities in the regular particles expressed on a mass% basis. At least 70% or more, preferably 90% or more, more preferably about 100% of the total functional group to be localized on the particle surface or its neighboring layers including the particle surface so that the functional group can be clearly identified. (Or uneven distribution). That is, such functional regular particles according to the present invention are obtained by growing seed particles by copolymerizing the (meth) acrylic monomer (A) under emulsion polymerization using the seed particles in an aqueous emulsion system as a nucleus. The copolymerizable monomer (B) has a polymerizable group and at least one functional group in the molecule, and the functional group is bonded to a hydrophobic group. Preferably, the hydrophobic group is a monomer molecule. A monomer having a specific molecular structure which is a polymerizable monomer (B) rich in hydrophobicity located at the molecular end of the polymer is suitable.

このような重合性モノマー（Ｂ）の官能基として、カルボキシル基、水酸基又はアミノ基が挙げられる。一方、少なくとも１種の官能基及び／又は置換基を分子内に有する重合性モノマー（Ｂ）において、その官能基又は置換基としては；例えば、カルボニル基，ビニル基，フェニル基，アミノ基，アミド基，イミド基，ヒドロキシル基，ハロゲン基，スルホン酸基，エポキシ基及びウレタン結合等を挙げることができる。本発明においては、このような重合性モノマー（Ｂ）における官能基又は置換基を有するモノマー種の単独又は２種以上の複数種を組合わせて適宜好適に使用することができる。
また、この重合性モノマー（Ｂ）の疎水基としては、炭素数Ｃが４以上の直鎖系又はフェニル系の疎水性基が挙げられ、また、この重合性モノマー（Ｂ）の重合性基として、ビニルメタクリル、アクリロイルが挙げられる。そこで、本発明において、このような疎水性の重合性モノマー（Ｂ）の具体例として、好ましくは、下記（１）〜（３）式で表される分子構造を有する重合性モノマーを適宜好適に用いることができる。 Examples of the functional group of the polymerizable monomer (B) include a carboxyl group, a hydroxyl group, and an amino group. On the other hand, in the polymerizable monomer (B) having at least one functional group and / or substituent in the molecule, examples of the functional group or substituent include: carbonyl group, vinyl group, phenyl group, amino group, amide Groups, imide groups, hydroxyl groups, halogen groups, sulfonic acid groups, epoxy groups and urethane bonds. In the present invention, such a polymerizable monomer (B) can be suitably used as appropriate, alone or in combination of two or more of the monomer species having a functional group or substituent.
In addition, examples of the hydrophobic group of the polymerizable monomer (B) include linear or phenyl hydrophobic groups having 4 or more carbon atoms, and examples of the polymerizable group of the polymerizable monomer (B). , Vinyl methacryl, and acryloyl. Therefore, in the present invention, as a specific example of such a hydrophobic polymerizable monomer (B), a polymerizable monomer having a molecular structure represented by the following formulas (1) to (3) is preferably used as appropriate. Can be used.

又は

Or

また、本発明において、重合性モノマー（Ｂ）に共重合させる（メタ）アクリル系モノマー（Ａ）は、その分子内に官能基及び／又は置換基を持たない帯電性が乏しいか又は無帯電性の傾向にある重合性モノマーであれば、適宜好適に用いられる。そのような（メタ）アクリル系モノマー（Ａ）として、例えば、アクリル酸アルキルエステルとしては；（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸プロピル，（メタ）アクリル酸イソプロピル，（メタ）アクリル酸ブチル，（メタ）アクリル酸イソブチル，（メタ）アクリル酸ペンチル，（メタ）アクリル酸ヘキシル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸オクチル，（メタ）アクリル酸ラウリル，（メタ）アクリル酸ノニル，（メタ）アクリル酸デシル，（メタ）アクリル酸ドデシル，（メタ）アクリル酸フェニル，（メタ）アクリル酸メトキシエチル，（メタ）アクリル酸エトキシエチル，（メタ）アクリル酸プロポキシエチル，（メタ）アクリル酸ブトキシエチル，（メタ）アクリル酸エトキシプロピル等が挙げられ、ジアルキルアミノアルキル（メタ）アクリレートとしては；ジエチルアミノエチル（メタ）アクリレート等が挙げられ、また、（メタ）アクリル酸アルコキシエステル類としては；（メタ）アクリル酸メトキシエチル，（メタ）アクリル酸エトキシエチル，（メタ）アクリル酸プロポキシエチル，（メタ）アクリル酸ブトキシエチル，（メタ）アクリル酸エトキシプロピル等が挙げられ、また、（ポリ）アルキレングリコールのジ（メタ）アクリル酸エステル類としては、エチレングリコールのジ（メタ）アクリル酸エステル，ジエチルグリコールのジ（メタ）アクリル酸エステル，トリエチレングリコールのジ（メタ）アクリル酸エステル，ポリエチレングリコールのジ（メタ）アクリル酸エステル，ジプロピレングリコールのジ（メタ）アクリル酸エステル，トリプロピレングリコールのジ（メタ）アクリル酸エステル等が挙げられ、また、多価（メタ）アクリル酸エステル類としては、トリメチロールプロパントリ（メタ）アクリル酸エステル等が挙げられる。さらに、（メタ）アクリル酸シクロヘキシル等の脂環式アルコールの（メタ）アクリル酸エステルが挙げられる。 In the present invention, the (meth) acrylic monomer (A) to be copolymerized with the polymerizable monomer (B) has poor chargeability without functional groups and / or substituents in the molecule, or is not charged. If it is the polymerizable monomer which has the tendency, it is used suitably suitably. Examples of such (meth) acrylic monomers (A) include, for example, alkyl acrylate esters; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , Butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Lauryl, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylic Propoxyethyl acid, butoxyethyl (meth) acrylate, (meth) Ethoxypropyl crylate and the like, and as dialkylaminoalkyl (meth) acrylate; diethylaminoethyl (meth) acrylate and the like, and as (meth) acrylic acid alkoxyesters; methoxyethyl (meth) acrylate , Ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, and the like, and (poly) alkylene glycol di (meth) acryl Acid esters include ethylene glycol di (meth) acrylic acid ester, diethyl glycol di (meth) acrylic acid ester, triethylene glycol di (meth) acrylic acid ester, polyethylene glycol di (meth) acrylic acid ester. Di (meth) acrylic acid ester of dipropylene glycol, di (meth) acrylic acid ester of tripropylene glycol and the like, and polyvalent (meth) acrylic acid esters include trimethylolpropane tri (meta ) Acrylic acid ester and the like. Furthermore, (meth) acrylic acid ester of alicyclic alcohol, such as (meth) acrylic acid cyclohexyl, is mentioned.

また、必要に応じて、その他に共重合させるモノマーとして、例えば、スチレン，メチルスチレン，ジメチルスチレン，トリメチルスチレン，エチルスチレン，ジエチルスチレン，トリエチルスチレン，プロピルスチレン，ブチルスチレン，ヘキシルスチレン，ヘプチルスチレン及びオクチルスチレン等のアルキルスチレン系モノマーが挙げられ、更には、その他の共重合性モノマーであるビニル基を有するモノマーとして、例えば、酢酸ビニル，プロピオン酸ビニル，ｎ−酪酸ビニル，イソ酪酸ビニル，ピバリン酸ビニル，カプロン酸ビニル，パーサティック酸ビニル，ラウリル酸ビニル，ステアリン酸ビニル，安息香酸ビニル，ｐ−ｔ−ブチル安息香酸ビニル，サリチル酸ビニル等のビニルエステル類が挙げることができる。 If necessary, other monomers to be copolymerized include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octyl. Examples of the monomer having a vinyl group, which is another copolymerizable monomer, include, for example, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, and vinyl pivalate. And vinyl esters such as vinyl caproate, vinyl caprosate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl salicylate.

以上から、本発明によれば、粒子表面に官能基が局在する機能性アクリル系ポリマー定形粒子を調製させるに、好ましくは、シード重合法で粒子成長させながら粒子形状として、真球状又は楕円球状の定形単分散粒子として適宜調製させることができる。 From the above, according to the present invention, in order to prepare functional acrylic polymer regular particles in which functional groups are localized on the particle surface, it is preferable that the particles are grown by seed polymerization while the particle shape is true spherical or elliptical spherical. Can be suitably prepared as regular monodisperse particles.

本発明においては、上記する（メタ）アクリル系モノマー（Ａ）から選ばれる１種又は２以上の混合モノマーの１００質量部当たり、上記する分子内に少なくとも１個の官能基を有し、且つ疎水性に富む上記（１）〜（３）式で表される重合性モノマー（Ｂ）の何れか１種のモノマーを１〜９０質量部の範囲で共重合させ、外観形状が真球状又は楕円球状の機能性定形アクリル系ポリマー粒子として調製される。本発明において、共重合させる疎水性の重合性モノマー（Ｂ）の反応量が下限値１以下では、官能基を粒子表面へ局在させ難いことから、好ましくなく、また、上限値の９０を超えると重合安定性、粒子形状を形成させ難いことから、好ましくない。従って、本発明において、好ましくは、５〜７０質量部で、更に好ましくは、１０〜６０質量部であることが好適である。また、このように調製される真球状又は楕円球状の定形単分散粒子は、電子顕微鏡法で表す平均粒子径が、２０ｎｍ〜５０μｍの範囲にある機能性アクリル系ポリマー定形粒子として適宜提供することができる。 In the present invention, per 100 parts by mass of one or two or more mixed monomers selected from the (meth) acrylic monomer (A) described above has at least one functional group in the molecule and is hydrophobic. One of the polymerizable monomers (B) represented by the above formulas (1) to (3), which is rich in properties, is copolymerized in the range of 1 to 90 parts by mass, and the external shape is a true sphere or an oval sphere Are prepared as functional regular acrylic polymer particles. In the present invention, if the reaction amount of the hydrophobic polymerizable monomer (B) to be copolymerized is not more than the lower limit value 1, it is not preferable because the functional group is difficult to localize on the particle surface, and the upper limit value of 90 is exceeded. Further, it is not preferable because it is difficult to form polymerization stability and particle shape. Therefore, in this invention, Preferably it is 5-70 mass parts, More preferably, it is suitable that it is 10-60 mass parts. In addition, the spherical or elliptical spherical monodisperse particles prepared in this way may be appropriately provided as functional acrylic polymer regular particles having an average particle diameter represented by an electron microscope in the range of 20 nm to 50 μm. it can.

そこで、このような本発明による機能性アクリル系ポリマー定形粒子は、既に上述するように、共重合させる疎水性の重合性モノマー（Ｂ）の官能基種によって、適宜（＋）帯電又は（−）帯電性粒子として調製される。その帯電性をブローオフ法による絶対値で表す表面帯電量Ｃ（μ・クーロン／ｇ）で表す数値として、１０≦｜Ｃ｜≦５００の範囲にある帯電性ポリマー定形粒子を適宜好適に提供することができる。 Thus, as described above, the functional acrylic polymer regular particles according to the present invention are appropriately (+) charged or (−) depending on the functional group type of the hydrophobic polymerizable monomer (B) to be copolymerized. Prepared as chargeable particles. Providing the charged polymer shaped particles in a range of 10 ≦ | C | ≦ 500 as the numerical value expressed by the surface charge amount C (μ · coulomb / g) expressed by the absolute value by the blow-off method as appropriate. Can do.

また、このように例えば、−ＣＯＯＨ、−ＮＨ_３、−ＯＨ等の官能基が粒子表面に多く頭出し状に局在していることから、この機能性アクリル系ポリマー定形粒子を用いて、イオン交換法で元素周期律表の第１族〜第１５族に属する金属元素及び遷移金属元素類から選ばれる少なくも１種の金属イオンを、適宜に担持させた金属イオン担持ポリマー定形粒子を提供することができる。 In addition, for example, since many functional groups such as —COOH, —NH ₃ , and —OH are localized on the surface of the particle, the functional acrylic polymer shaped particles are used to form ions. Provided is a metal ion-supported polymer shaped particle in which at least one metal ion selected from metal elements and transition metal elements belonging to Groups 1 to 15 of the Periodic Table of Elements is appropriately supported by an exchange method. be able to.

また、このように官能基が粒子表面に多く頭出し状に局在している本発明による機能性アクリル系ポリマー定形粒子を用いれば、従来のように重合反応時に、形成粒子内に染料を抱え込み内包させる染料内包型着色ではなく、この粒子表面に頭出し状に局在する官能基種を介して、通常の染色法で、有彩色に又は無彩色の黒色に粒子表面の近傍相を含む粒子表面を効果的に染色させられる。このように染色着色された球状着色粒子は、ファクシミリ、複写機、レーザプリンター等電子写真画像形成用の静電トナー定形粒子として適宜提供することができる。 In addition, when the functional acrylic polymer regular particles according to the present invention in which many functional groups are localized on the surface of the particle in this way are used, the dye is held in the formed particles during the polymerization reaction as in the past. Particles containing a phase near the particle surface in a chromatic or achromatic black color by a normal dyeing method via a functional group species localized in the form of a head on the surface of the particle, rather than a dye-encapsulated coloring to be included The surface can be effectively dyed. The spherically colored particles thus dyed and colored can be appropriately provided as electrostatic toner regular particles for forming an electrophotographic image such as a facsimile, a copying machine, and a laser printer.

また、本発明による機能性アクリル系ポリマー定形粒子としての染色法で有彩色に又は無彩色の黒色に染色着色された球状粒子をボールペンインクやその他の着色材に、また、特に黒色に染色着色された球状粒子は画像表示装置に用いられる遮光性粒子に、また、特に、染色法で黒色系無彩色に染色着色された電子顕微鏡法で表す平均粒子径が１００〜５００ｎｍの単分散の球状粒子は構造色形成用の黒色系無彩色球状粒子としてそれぞれ適宜好適に提供することができる。必要に応じて、エマルジョンに分散する着色樹脂微粒子を分離回収し、再度このナノサイズの着色粒子を水性媒体中に再分散させて、既に公知のインクジェットプリンター用インク、印刷用水性インク、筆記用水性インク及びスタンプ用インク等の水性インクや、感熱記録紙用発色剤、感温色材、コーティング剤、水性塗料及び化粧料、カラーフィルタ等に、この着色樹脂微粒子や、この着色水性エマルジョン組成物を適宜好適に用いることができる。また、その表面の特定量の官能基に係わって、その表面のイオン交換性及び化学的活性を利用したクロマトカラム充填材として適宜好適に用いられる。 In addition, spherical particles dyed and colored in chromatic or achromatic black by the dyeing method as the functional acrylic polymer regular particles according to the present invention are dyed and colored in ballpoint pen ink and other coloring materials, and particularly in black. The spherical particles are the light-shielding particles used in the image display device, and in particular, the monodispersed spherical particles having an average particle diameter of 100 to 500 nm expressed by an electron microscope dyed and colored in a black achromatic color by a staining method are Each of them can be suitably provided as black achromatic spherical particles for forming a structural color. If necessary, the colored resin fine particles dispersed in the emulsion are separated and recovered, and then the nano-sized colored particles are re-dispersed in an aqueous medium, and the ink-jet printer ink, printing water-based ink, writing water-based ink are already known. The colored resin fine particles and the colored aqueous emulsion composition are applied to water-based inks such as ink and stamp ink, color formers for thermal recording paper, temperature-sensitive color materials, coating agents, water-based paints and cosmetics, and color filters. It can use suitably suitably. Moreover, it relates to a specific amount of functional groups on the surface, and is suitably used as a chromatographic column packing material utilizing the ion exchange property and chemical activity of the surface.

また、更には、このような本発明による帯電性着色樹脂微粒子は、例えば、電子写真画像装置の電界系で用いられ所望する帯電性の静電着色トナーとして、また、ＰＬＤに用いられて所望する帯電性、電気泳動性を発揮させてＰＬＤ用の画像表示及び／又は印字表示のディスプレイ帯電性着色粒子として提供することができる。 Further, such a chargeable colored resin fine particle according to the present invention is used, for example, as a desired chargeable electrostatic color toner used in an electric field system of an electrophotographic image apparatus, or in a PLD. It can be provided as display chargeable colored particles for PLD image display and / or print display by exhibiting chargeability and electrophoretic properties.

そこで、本発明による機能性アクリル系ポリマー定形粒子を用いる染料着色は、既に上述する如く、従来のように重合反応時に重合形成粒子内に重合モノマーに溶解させた染料を抱え込み内包させる染料内包型着色ではなく、この粒子表面に頭出し状に局在する官能基に係わる粒子表面特性を介して、染料溶解液に粒子を浸漬させる通常の染色法で適宜好適に染色着色することができることが特徴である。本発明において染料として、例えば、黒色のSolvent Black 27Cr（３価）５％含有，Pigment Black７／水、赤色のSolvent Red132,Solvent Red8Cr（３価）５．８％含有、青色のSolvent Blue 35、黄色のＳolvent Yellow16，Solvent Yellow33，Disperse Yellow 54、緑色のSolvent Green3、マゼンダのDisperse Violet 28，Solvent Red149，Solvent Red49，Solvent Red 52，Solvent Red218Cr（３価）４％含有、シアンのSolvent Blue70Cu４％含有、オレンジのSolvent Orange 70，Solvent Orange 6、ブラウンのSolvent Yellow116等を挙げることができる。また、例えば、ソルベントブルー，ソルベントレッド，ソルベントオレンジ，ソルベントグリーン，ルモゲンＦオレンジー等が挙げられる。また、例えば、クラリン系、ペリレン系、ジシアノピニル系、アゾ系、キノフタロン系、アミノピラゾール系、メチン系、ジシアノイミダゾール系、インドアニリン系、フタロシアニン系等の筆記記録液に通常使用されている染料や、感熱記録紙や感温色材として用いられるロイコ染料や、また、例えば、ローダミンＢステアレート（赤色２１５号），テトラクロルテトラブロムフルオレセン（赤色２１８号），テトラブロムフルオレセン（赤色２２３号），スダンIII（赤色２２５号），ジブロムフルオレセイン（橙色２０１号），ジヨードフルオレセイン（橙色２０６号），フルオレセイン（黄色２０１号），キノリンエローＳＳ（黄色２０４号），キニザリングリーンＳＳ（緑色２０２号），アズリンパープルＳＳ（紫色２０１号），薬用スカーレット（赤色５０１号），オイルレッドＸＯ（赤色５０５号），オレンジＳＳ（橙色４０３号），エローＡＢ（黄色４０４号），エローＯＢ（黄色４０５号），スダンブルーＢ（青色４０３号）等の化粧品に使用されているタール系染料をも挙げることができる。本発明において、これらの染料の単独又は２種以上を混合させて使用され、また、必要に応じて各種の直接染料、酸性染料、塩基性染料、アゾイック染料、反応性染料、蛍光染料及び蛍光増白剤等を所望する色調等に応じて適宜選んで使用することができる。 Therefore, the dye coloring using the functional acrylic polymer regular particles according to the present invention is, as described above, the dye-containing coloring in which the dye dissolved in the polymerization monomer is held in the polymerization forming particle during the polymerization reaction as described above. Rather, it is characterized in that it can be suitably dyed and colored appropriately by a normal dyeing method in which particles are immersed in a dye solution through the particle surface properties related to the functional groups localized in the form of heads on the particle surface. is there. Examples of the dye in the present invention include black Solvent Black 27Cr (trivalent) 5%, Pigment Black 7 / water, red Solvent Red132, Solvent Red8Cr (trivalent) 5.8%, blue Solvent Blue 35, yellow Solvent Yellow 16, Solvent Yellow 33, Disperse Yellow 54, Green Solvent Green 3, Magenta Disperse Violet 28, Solvent Red 149, Solvent Red 49, Solvent Red 52, Solvent Red 218Cr (trivalent) 4%, cyan Solvent Blue 70Cu 4%, orange Solvent Orange 70, Solvent Orange 6, Brown Solvent Yellow 116, and the like. Moreover, for example, solvent blue, solvent red, solvent orange, solvent green, rumogen F orange and the like can be mentioned. In addition, for example, dyes commonly used in writing recording liquids such as clarine, perylene, dicyanopinyl, azo, quinophthalone, aminopyrazole, methine, dicyanoimidazole, indoaniline, phthalocyanine, A leuco dye used as a heat-sensitive recording paper or a temperature-sensitive color material, and, for example, rhodamine B stearate (red 215), tetrachlorotetrabromofluoresene (red 218), tetrabromofluorescene (red 223) No.), Sudan III (red No. 225), dibromofluorescein (orange No. 201), diiodo fluorescein (orange No. 206), fluorescein (yellow No. 201), quinoline yellow SS (yellow No. 204), quinizarin green SS ( Green 202), azurin purple SS (purple 201), medicine Cosmetics such as Scarlet (Red 501), Oil Red XO (Red 505), Orange SS (Orange 403), Yellow AB (Yellow 404), Yellow OB (Yellow 405), Sudan Blue B (Blue 403) The tar-type dye currently used for can also be mentioned. In the present invention, these dyes are used alone or in admixture of two or more, and various direct dyes, acid dyes, basic dyes, azoic dyes, reactive dyes, fluorescent dyes and fluorescent dyes are used as necessary. A whitening agent or the like can be appropriately selected and used according to a desired color tone.

以上から、本発明によれば、粒子中に含有する官能基に係わって各種の機能性を発揮させる官能基が、粒子表面又は粒子表面を含むその近傍相に頭出しするように局在していることを特徴とする機能性アクリル系ポリマー定形粒子であって、以下にその代表的な製造方法について説明する。 From the above, according to the present invention, the functional group that exerts various functions in relation to the functional group contained in the particle is localized so as to cue up to the particle surface or its neighboring phase including the particle surface. In the following, a typical production method for the functional acrylic polymer shaped particles characterized by the above will be described.

その製造方法においては、先ずソープフリー乳化重合で、平均粒子径０．１〜３μｍの範囲にある好ましくは、略球状で、更に好ましくは略単分散粒子のシード粒子を調製する。その粒子は固形分としての分散濃度が、２０〜４０質量％の範囲で分散する水系分散液として調製する。そこで、一次樹脂粒子がアクリル系であって、例えば（メタ）アクリル系モノマーのメチルメタクリレート（ＭＭＡ）の１００質量部当たり、水２００〜３５０質量部の範囲にある水を含有する系を、窒素雰囲気の攪拌下に加温させて、０．３〜０．６質量部の範囲で過硫酸カリウムを添加させて加温下に重合させ、平均粒子径０．１〜０．５μｍの略一定の粒子径を有する球状の重合体粒子の固形分としての分散濃度が２０〜４０質量％である水系分散液を調製する。次いで、別途に、強攪拌下にＭＭＡの８０〜９５質量部に、０．８〜１．２質量部の範囲で過酸化ベンゾイルを入れて溶解させた後、強攪拌下に１８０〜２５０質量部の範囲で水と、３．０〜４．０質量部の範囲のポリオキシエチレン多環フェニルエーテル硫酸エステル塩の乳化剤及び０．０５〜０．１５質量部の範囲での亜硝酸ナトリウム（ＵＮＡ−Ｎａ）とを混合させる。次いで、上記水系分散液の２８〜３５質量部を添加後、緩やかな攪拌下に５０〜８０℃範囲で重合反応させて、平均粒径０．４〜１．０μｍで、固形分濃度として２５〜３５質量％であるシード粒子の水系分散液を調製できる。次いで、同様に繰り返し、平均粒径１．５〜３μｍで、固形分濃度として３０〜３５質量％であるシード粒子の水系分散液を調製する。 In the production method, first, seed particles having an average particle size in the range of 0.1 to 3 μm, preferably approximately spherical, and more preferably approximately monodisperse particles are prepared by soap-free emulsion polymerization. The particles are prepared as an aqueous dispersion in which the dispersion concentration as a solid content is in the range of 20 to 40% by mass. Therefore, a system in which the primary resin particles are acrylic and contains water in the range of 200 to 350 parts by mass of water per 100 parts by mass of (meth) acrylic monomer methyl methacrylate (MMA), for example, in a nitrogen atmosphere. The particles are heated under stirring, added with potassium persulfate in the range of 0.3 to 0.6 parts by mass, polymerized under heating, and substantially constant particles having an average particle size of 0.1 to 0.5 μm. An aqueous dispersion having a dispersion concentration of 20 to 40% by mass as a solid content of spherical polymer particles having a diameter is prepared. Then, separately, benzoyl peroxide was added and dissolved in 80 to 95 parts by mass of MMA in the range of 0.8 to 1.2 parts by mass with strong stirring, and then 180 to 250 parts by mass with strong stirring. Water, an emulsifier of polyoxyethylene polycyclic phenyl ether sulfate in the range of 3.0 to 4.0 parts by mass and sodium nitrite (UNA- in the range of 0.05 to 0.15 parts by mass). Na). Next, after adding 28 to 35 parts by mass of the above aqueous dispersion, the polymerization reaction is carried out in the range of 50 to 80 ° C. with gentle stirring to obtain an average particle size of 0.4 to 1.0 μm and a solid content concentration of 25 to 25%. An aqueous dispersion of 35% by weight seed particles can be prepared. Subsequently, an aqueous dispersion of seed particles having an average particle size of 1.5 to 3 μm and a solid content concentration of 30 to 35% by mass is prepared in the same manner.

次いで、このシード粒子の水系分散体を用いて、（メタ）アクリル系モノマー（Ａ）の１００質量部当たり、少なくとも１個の官能基を有し、且つ疎水性に富む上記（１）〜（３）式で表される重合性モノマー（Ｂ）の何れか１種のモノマーを１〜９０質量部の範囲で共重合させ、外観形状が真球状又は楕円球状の機能性定形アクリル系ポリマー粒子として調製する。 Then, using the aqueous dispersion of seed particles, the above (1) to (3) having at least one functional group and rich in hydrophobicity per 100 parts by mass of the (meth) acrylic monomer (A). ) Any one of the polymerizable monomers (B) represented by the formula is copolymerized in the range of 1 to 90 parts by mass, and prepared as functional regular acrylic polymer particles having a true or oval appearance. To do.

すなわち、（メタ）アクリル系モノマーである例えば、メチルメタクリレート（ＭＭＡ）の１００質量部当たり、架橋剤のエチレングリコールジメタクリレートの２．５〜３．６質量部と、上記重合性モノマー（Ｂ）の３０〜４０質量部と、過酸化ベンゾイルの０．５〜０．９質量部と、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）の１〜２質量部と、水２６０〜４６０質量部と、乳化剤のポリオキシエチレン多環フェニルエーテル硫酸エステル塩の１２〜１８質量部及び亜硝酸ナトリウムの０．１２〜０．１８とを加え強攪拌下に混合し、次いで、上記シード粒子の水系分散体の１００〜１２０質量部を添加し、攪拌下の４０〜８０℃×１〜２時間反応させて平均粒径３〜５μｍの範囲にある固形分濃度２５〜３５質量％の本発明による真球状又は楕円球状の機能性定形アクリル系ポリマー粒子を調製する。 That is, for example, per 100 parts by mass of methyl methacrylate (MMA) which is a (meth) acrylic monomer, 2.5 to 3.6 parts by mass of ethylene glycol dimethacrylate as a crosslinking agent, and the polymerizable monomer (B) 30-40 parts by weight, 0.5-0.9 parts by weight of benzoyl peroxide, 1-2 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate), and 260-460 water Add parts by weight of 12 to 18 parts by weight of polyoxyethylene polycyclic phenyl ether sulfate salt of emulsifier and 0.12 to 0.18 of sodium nitrite and mix under strong stirring. 100 to 120 parts by mass of the aqueous dispersion was added, and the mixture was reacted at 40 to 80 ° C. for 1 to 2 hours under stirring, with a solid content concentration in the range of 3 to 5 μm in average particle size of 25 to 35% by mass. True spherical or elliptic spherical functional regular acrylic polymer particles according to the present invention are prepared.

また、重合開始剤としては、例えば、シード粒子を調製するに際しては、過硫酸カリウム，過硫酸アンモニウム等の過硫酸塩、過酸化ベンゾイル、過酸化ラウリウム等の過酸化物、アソビスイソブチロニトリル等のアゾ化合物等が挙げられる。また、重合時に好ましく用いられる重合開始剤として、例えば、アゾ系重合開始剤としては、２，２’−アゾビス（２−メチルプロポピオニトリル）、２，２’−アゾビス（２−メチルブチロルニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−ジクロプロピルプロピオニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）等が挙げられる。 As the polymerization initiator, for example, when preparing seed particles, persulfates such as potassium persulfate and ammonium persulfate, peroxides such as benzoyl peroxide and laurium peroxide, asobisisobutyronitrile, etc. An azo compound etc. are mentioned. Moreover, as a polymerization initiator preferably used at the time of superposition | polymerization, as an azo polymerization initiator, for example, 2,2'-azobis (2-methylpropopionitrile), 2,2'-azobis (2-methylbutyronitrile) ), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-dichloropropylpropionitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl -2,2'-azobis (2-methylpropionate) and the like.

また、乳化剤としては、通常に使用されているアニオン系界面活性剤、カチオン系界面活性剤又は必要に応じてノニオン系界面活性剤等から選んで、その単独又は組合わせて使用することができる。例えば、アニオン系界面活性剤としてはドデシルベンゼンスルホネート、ドデシルベンゼンスルホネート、ウンデシルベンゼンスルホネート、トリデシルベンゼンスルホネート、ノニルベンゼンスルホネート、これらのナトリウム、カリウム塩等が挙げられ、また、カチオン系界面活性剤としてはセチルトリメチルアンモニウムプロミド、塩化ヘキサデシルピリジニウム、塩化ヘキサデシルトリメチルアンモニウム等が挙げられ、また、ノニオン系界面活性剤としては、リピリジニウム等が挙げられる。また、反応性乳化剤（例えば、アクリロイル基、メタクロイル基等の重合性基を有する乳化剤）としては、例えば、アニオン性、カチオン性又はノニオン性の反応性乳化剤が挙げられ、特に限定することなく使用されるが、アニオン性の反応性乳化剤が好適に使用され、例えば、スルホン酸（塩）型、カルボン酸（塩）型、リン酸エステル型等が挙げられ、具体的には、例えば、ポリオキシエチレンアリルグリシジルノニルフェニルエーテルの硫酸塩、ポリオキシエチレンノニルプロペニルエーテルの硫酸エステル塩等が挙げられる。 Moreover, as an emulsifier, it can select from the anionic surfactant normally used, a cationic surfactant, or a nonionic surfactant as needed, and can use it individually or in combination. Examples of anionic surfactants include dodecyl benzene sulfonate, dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, nonyl benzene sulfonate, sodium and potassium salts thereof, and cationic surfactants. Cetyltrimethylammonium promide, hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride and the like, and nonionic surfactants include lipidinium and the like. Examples of reactive emulsifiers (for example, emulsifiers having a polymerizable group such as acryloyl group, methacryloyl group) include anionic, cationic or nonionic reactive emulsifiers, and are used without particular limitation. However, anionic reactive emulsifiers are preferably used, and examples thereof include sulfonic acid (salt) type, carboxylic acid (salt) type, and phosphoric ester type. Specifically, for example, polyoxyethylene Examples thereof include sulfates of allyl glycidyl nonyl phenyl ether and sulfates of polyoxyethylene nonyl propenyl ether.

また、重合時に好ましく用いられる乳化剤として、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩，ポリエチレングリコールノニルフェニルエーテル等のポリエチレングリコールアルキルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン多環フェニルエーテル、アリルエテール及びその硫酸塩等を挙げることができる。そこで、これらの乳化剤は、シード粒子を調製するに際しては、単量体１００質量部当たり、通常、０．０１〜５質量部の範囲であってよく、また、重合時に際しては、特に、重合性モノマー（Ａ）及び重合性モノマー（Ｂ）の合量単量体１００質量部当たり、０．０１〜５０で、好ましくは、３〜２０であれば好適である。 Further, as an emulsifier preferably used at the time of polymerization, alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate, polyethylene glycol alkyl ether such as polyethylene glycol nonylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polycyclic phenyl ether, allyl ether and The sulfate etc. can be mentioned. Therefore, these emulsifiers may be usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of the monomer when preparing the seed particles, and are particularly polymerizable during the polymerization. It is 0.01 to 50, preferably 3 to 20 per 100 parts by mass of the total monomer of the monomer (A) and the polymerizable monomer (B).

また、このような染料の２段階固定化法を効果的に進捗させるために、染料親水化助剤を添加させて油溶性染料を内包又はその表層に固定させている。このような染料親水化助剤としては、本発明において、水溶性有機溶媒であるメタノール、エタノール、プロパノール、イソプロパノール、アセトン、メチルエチルケトン及びテトラヒドロフラン等を挙げることができる。これらの染料親水化助剤の添加量は、所望する油溶性染料の固定量及びその種類によっても異なるので特に限定されないが、本発明においては質量基準で、添加する油溶性染料の１００質量部に対して、染料親水化助剤の０〜１０質量部、好ましくは、０．０５〜９質量部を適宜添加することができる。 Further, in order to effectively advance such a two-stage fixing method of the dye, a dye hydrophilic agent is added to fix the oil-soluble dye in the inner layer or the surface layer thereof. Examples of such a dye hydrophilization aid include water-soluble organic solvents such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, and tetrahydrofuran in the present invention. The amount of these dye hydrophilization aids added is not particularly limited because it varies depending on the desired fixed amount of oil-soluble dye and its type, but in the present invention, it is added to 100 parts by weight of the oil-soluble dye to be added. On the other hand, 0 to 10 parts by mass, preferably 0.05 to 9 parts by mass of the dye hydrophilization aid can be appropriately added.

また、本発明においては、必要に応じてそれ自体公知のその他の添加剤（配合剤）である、例えば、熱安定剤、分散剤、防腐剤、消泡剤、防錆剤、酸化防止剤、帯電防止剤、近赤外吸収剤、紫外線吸収剤、光安定剤、蛍光剤、蛍光増白剤等をそれ自体公知の処方によって添加・分散させることができる。これらの添加剤は、上述する如く着色樹脂微粒子に内包、又は表面に被覆させて用いられるし、また、このように調製される重合体粒子が分散するエマルジョン中に分散又は溶解させて、そのまま分離することなく適宜添加させることができる。また、これらのＩＪプリンター用インク、印刷用水性インク、筆記用水性インク及びスタンプ用インク等の水性インクや、感熱記録紙用発色剤、感温色材、コーティング剤、水性塗料及び各種の化粧料等の用途には、それぞれ周知の添加剤を上述する添加剤から適宜選んで添加させて調製することができる。 Further, in the present invention, other additives known per se as necessary (compounding agents), for example, heat stabilizers, dispersants, preservatives, antifoaming agents, rust preventives, antioxidants, Antistatic agents, near-infrared absorbers, ultraviolet absorbers, light stabilizers, fluorescent agents, fluorescent brighteners, and the like can be added and dispersed according to a formulation known per se. These additives are used by being encapsulated or coated on the surface of colored resin fine particles as described above, and are dispersed or dissolved in an emulsion in which the polymer particles thus prepared are dispersed and separated as they are. It can add suitably, without doing. In addition, water-based inks such as these inks for IJ printers, water-based inks for printing, water-based inks for writing, and inks for stamps, colorants for thermal recording paper, temperature-sensitive color materials, coating agents, water-based paints, and various cosmetics For such applications, known additives can be prepared by appropriately selecting from the above-mentioned additives.

以下に、本発明を実施例により説明するが、本発明は、これらの実施例にいささかも限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

（参考例）
ソープフリー乳化重合によって、温度計と窒素導入管とを装着した容量１リットルの四つ口フラスコに、単量体であるメチルメタクリレート（ＭＭＡ）１００質量部と水３００質量部とを投入して撹拌混合し、さらに窒素雰囲気下で撹拌を行いながら８０℃に昇温させ、次いで混合液中に過硫酸カリウム０．５質量部を加え、８０℃で約６時間反応させて重合体固形分として２６．５質量％の分散体（１）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は０．４μｍであった。 (Reference example)
By soap-free emulsion polymerization, 100 parts by mass of monomer methyl methacrylate (MMA) and 300 parts by mass of water are stirred into a 1 liter four-necked flask equipped with a thermometer and a nitrogen inlet tube. Then, the mixture was heated to 80 ° C. with stirring under a nitrogen atmosphere, 0.5 parts by mass of potassium persulfate was added to the mixed solution, and the mixture was reacted at 80 ° C. for about 6 hours to obtain a polymer solid content of 26. A dispersion (1) of 0.5 mass% was obtained. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 0.4 μm.

次いで、同様の容量１リットルの四つ口フラスコに、ＭＭＡ９１．７７質量部と過酸化ベンゾイル１．０質量部とを投入して溶解させ、更にこの溶液に水２００質量部と、ポリオキシエチレン系フェニルエーテル硫酸エステル塩３．３質量部、亜硝酸ナトリウム０．１１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（１）３１．３３質量部を添加させて、攪拌下の５０〜７５℃で反応させて重合体固形分として３１質量％の分散体（２）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は０．９μｍであった。 Next, 91.77 parts by mass of MMA and 1.0 part by mass of benzoyl peroxide are charged into a similar one-liter four-necked flask and dissolved, and 200 parts by mass of water and polyoxyethylene-based solution are added to this solution. 3.3 parts by mass of phenyl ether sulfate ester salt and 0.11 parts by mass of sodium nitrite were added and mixed with vigorous stirring. Next, 31.33 parts by mass of the above dispersion (1) was added to this mixed solution and reacted at 50 to 75 ° C. with stirring to obtain a dispersion (2) having a polymer solid content of 31% by mass. . When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 0.9 μm.

次いで、同様の装置にＭＭＡ９５質量部と過酸化ベンゾイル１．０質量部とを投入し、更にこの溶液に水２００質量部と、ポリオキシエチレン系フェニルエーテル硫酸エステル塩３．３質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に、上記の分散体（２）１６．１質量部を添加し、攪拌下の５０〜７５℃で反応させて重合体固形分として３２．５質量％の分散体（３）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は２．４１μｍであった。 Next, 95 parts by mass of MMA and 1.0 part by mass of benzoyl peroxide were charged into the same apparatus. Further, 200 parts by mass of water, 3.3 parts by mass of polyoxyethylene phenyl ether sulfate ester salt, Sodium nitrate 0.1 part by mass was added and mixed with vigorous stirring. Next, 16.1 parts by mass of the above dispersion (2) is added to this mixed solution and reacted at 50 to 75 ° C. with stirring to obtain 32.5% by mass of the dispersion (3) as a polymer solid content. Obtained. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 2.41 μm.

（実施例１）
同様の容量１リットルの反応装置に、ＭＭＡ５８質量部、エチレングリコールジメタクリレート２質量部、本発明における疎水性に富む重合性モノマー（Ｂ）であるジエチルアミノメチルメタクリレート２０質量部を投入し、次いで過酸化ベンゾイル０．５質量部と、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）１．０質量部を投入して溶解させ、更に、この溶液に水２５０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（３）６６．６質量部を添加させ、攪拌下の５０〜７８℃で約１．５時間反応させて重合体固形分として３０質量％の本発明の機能性アクリル系ポリマー定形粒子である表面官能基がアミノ基で、架橋された定形粒子の分散体（４）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は４．１μｍであった。次いでこのエマルジョン分散体を濾過・乾燥・粉化させ、得られた粉体の鉄に対する帯電量を測定した結果、３０μＣ／ｇ（マイクロクーロン／グラム）（表３に示す）であった。なお、帯電量測定は（キャリア粉体として、還元鉄粉ＴＥＦＶ−２００．３００を用いて測定を行った。） (Example 1)
Into a similar 1 liter reactor, 58 parts by mass of MMA, 2 parts by mass of ethylene glycol dimethacrylate, and 20 parts by mass of diethylaminomethyl methacrylate, which is a polymerizable monomer (B) rich in hydrophobicity according to the present invention, are then introduced. 0.5 parts by mass of benzoyl and 1.0 parts by mass of dimethyl-2,2′-azobis (2-methylpropionate) are added and dissolved. Further, 250 parts by mass of water and 10 parts by mass of oxyethylene polycyclic phenyl ether sulfate ester salt and 0.1 part by mass of sodium nitrite were added and mixed with strong stirring. Next, 66.6 parts by mass of the above dispersion (3) was added to this mixed solution, and the mixture was reacted at 50 to 78 ° C. with stirring for about 1.5 hours, so that the polymer solid content was 30% by mass. A dispersion (4) of cross-linked regular particles in which the surface functional groups, which are conductive acrylic polymer regular particles, are amino groups is obtained. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 4.1 μm. Next, this emulsion dispersion was filtered, dried and pulverized, and the charge amount of the obtained powder with respect to iron was measured. As a result, it was 30 μC / g (microcoulomb / gram) (shown in Table 3). In addition, the charge amount measurement (measured using a reduced iron powder TEFV-200.300 as a carrier powder).

（実施例２）
同様の容量１リットルの反応装置に、ＭＭＡ５８質量部、エチレングリコールジメタクリレート２質量部、本発明における疎水性に富む重合性モノマー（Ｂ）であるβ−メタクリロイルオキシエチルハイドロジェンフタレート２０質量部を投入し、次いで過酸化ベンゾイル０．５質量部と、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）１．００質量部を投入して溶解させ、更に、この溶液に水２５０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（３）６６．６質量部を添加させ、攪拌下の５０〜７８℃で約１．５時間反応させた後、９０℃で約１．５時間熟成させて重合体固形分として３１質量％の本発明の機能性アクリル系ポリマー定形粒子である表面官能基がカルボキシル基で、架橋された定形粒子の分散体（５）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は４．１μｍであった。次いでこのエマルジョン分散体を濾過・乾燥・粉化させ、得られた粉体の鉄に対する帯電量を測定した結果、−５９μＣ／ｇ（表３に示す）であった。 (Example 2)
A similar 1 liter reactor is charged with 58 parts by mass of MMA, 2 parts by mass of ethylene glycol dimethacrylate, and 20 parts by mass of β-methacryloyloxyethyl hydrogen phthalate, which is a polymerizable monomer (B) rich in hydrophobicity in the present invention. Then, 0.5 part by mass of benzoyl peroxide and 1.00 part by mass of dimethyl-2,2′-azobis (2-methylpropionate) were added and dissolved, and 250 parts by mass of water was further added to this solution. Then, 10 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier and 0.1 part by mass of sodium nitrite were added and mixed with strong stirring. Next, 66.6 parts by mass of the above dispersion (3) was added to this mixed solution, and the mixture was reacted at 50 to 78 ° C. with stirring for about 1.5 hours, and then aged at 90 ° C. for about 1.5 hours. The dispersion (5) of the regular particle which cross-linked the surface functional group which is the functional acrylic polymer regular particle of this invention of 31 mass% as a polymer solid content by the carboxyl group was obtained. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 4.1 μm. Next, this emulsion dispersion was filtered, dried and pulverized, and the charge amount of the obtained powder with respect to iron was measured. As a result, it was -59 μC / g (shown in Table 3).

（実施例３）
同様の容量１リットルの反応装置に、ＭＭＡ５８質量部、エチレングリコールジメタクリレート２質量部、本発明における疎水性に富む重合性モノマー（Ｂ）であるフェニルグリシジルエーテルアクリレート２０質量部を投入し、次いでジメチル−２，２’−アゾビス（２−メチルプロピオネート）５．０質量部溶解させ、更にこの溶液に水２５０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（３）６６．６質量部を添加させ、攪拌下の５０〜７８℃で約２時間反応させた後、９０℃で約３時間熟成させて重合体固形分として３１質量％の本発明の機能性アクリル系ポリマー定形粒子である表面官能基がヒドロキシル基で、架橋された定形粒子の分散体（６）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は３．９μｍであった。次いでこのエマルジョン分散体を濾過・乾燥・粉化させ、得られた粉体の鉄に対する帯電量を測定した結果、−２２０μＣ／ｇ（表３に示す）であった。 (Example 3)
In a similar 1 liter reactor, 58 parts by mass of MMA, 2 parts by mass of ethylene glycol dimethacrylate, and 20 parts by mass of phenylglycidyl ether acrylate, which is a polymerizable monomer (B) rich in hydrophobicity in the present invention, are added. -2,2'-azobis (2-methylpropionate) 5.0 parts by mass, and further, 250 parts by mass of water and 10 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier, Sodium nitrite 0.1 part by mass was added and mixed with vigorous stirring. Next, 66.6 parts by mass of the above dispersion (3) was added to this mixed solution, reacted at 50 to 78 ° C. for about 2 hours with stirring, and then aged at 90 ° C. for about 3 hours to obtain a polymer solid content. As a result, there was obtained a dispersion (6) of shaped particles which were 31% by mass of the functional acrylic polymer shaped particles of the present invention and whose surface functional groups were hydroxyl groups and were crosslinked. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 3.9 μm. Next, this emulsion dispersion was filtered, dried and powdered, and the charge amount of the obtained powder with respect to iron was measured. As a result, it was -220 μC / g (shown in Table 3).

（実施例４）
同様の容量１リットルの反応装置に、ＭＭＡ６０質量部、本発明における疎水性に富む重合性モノマー（Ｂ）であるジエチルアミノメチルメタクリレート２０質量部を投入し、次いで過酸化ベンゾイル０．５５質量部と、ジメチル−２，２’−アゾビス（２−メチルプロピオネート）１．０質量部を投入して溶解させ、更に、この溶液に水２５０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（３）６６．６質量部を添加させ、攪拌下の５０〜７８℃で約１．５時間反応させた後、９０℃で約１．５時間熟成させて重合体固形分として３０質量％の本発明の機能性アクリル系ポリマー定形粒子である表面官能基がアミノ基で、架橋されていない未架橋定形粒子の分散体（７）を得た。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は４．１μｍであった。次いでこのエマルジョン分散体を濾過・乾燥・粉化させ、得られた粉体の鉄に対する帯電量を測定した結果、３３μＣ／ｇであった。 (Example 4)
In a similar 1 liter reactor, 60 parts by mass of MMA and 20 parts by mass of diethylaminomethyl methacrylate which is a polymerizable monomer (B) rich in hydrophobicity in the present invention were added, and then 0.55 parts by mass of benzoyl peroxide, 1.0 part by mass of dimethyl-2,2′-azobis (2-methylpropionate) is added and dissolved, and further 250 parts by mass of water and polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier are added to this solution. 10 parts by mass of salt and 0.1 part by mass of sodium nitrite were added and mixed with strong stirring. Next, 66.6 parts by mass of the above dispersion (3) was added to this mixed solution, and the mixture was reacted at 50 to 78 ° C. with stirring for about 1.5 hours, and then aged at 90 ° C. for about 1.5 hours. A dispersion (7) of uncrosslinked regular particles that were 30% by mass as the polymer solid content of the functional acrylic polymer regular particles of the present invention and whose surface functional group was an amino group and was not crosslinked was obtained. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 4.1 μm. Next, this emulsion dispersion was filtered, dried and pulverized, and the charge amount of the obtained powder to iron was measured. As a result, it was 33 μC / g.

（実施例５）
実施例５−１として、同様の容量１リットルの反応装置に、ＭＭＡ５８質量部、エチレングリコールジメタクリレート１質量部、本発明における疎水性に富む重合性モノマー（Ｂ）であるジエチルアミノメチルメタクリレート２０質量部を投入し、次いでジメチル−２，２’−アゾビス（２−メチルプロピオネート）５．０質量部、銅フタロシアニン系染料（Ｃ．Ｉソルベントブルー７０）の２質量部を投入して溶解させ、更にこの溶液に水２５０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部と、亜硝酸ナトリウム０．１質量部を加え強撹拌混合させた。次いでこの混合溶液に上記の分散体（３）の６６．６質量部を添加させ、攪拌下の５０〜７８℃で約２時間反応させた後、９０℃で約３時間熟成させて重合体固形分として３１質量％の分散体（８）を得た。すなわち、官能基がアミノ基であるこのような重合性モノマー（Ｂ）が介在する系で、従来のように重合反応持に、形成粒子内に染料を抱え込み内包させた染料内包型シアン着色粒子を調製した。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は３．９μｍであった。次いでこのエマルジョン分散体を濾過・乾燥・粉化させ、得られた粉体の鉄に対する帯電量を測定した結果、３３μＣ／ｇであった。 (Example 5)
As Example 5-1, in a similar 1 liter reactor, 58 parts by mass of MMA, 1 part by mass of ethylene glycol dimethacrylate, 20 parts by mass of diethylaminomethyl methacrylate which is a polymerizable monomer (B) rich in hydrophobicity in the present invention. Then, 5.0 parts by mass of dimethyl-2,2′-azobis (2-methylpropionate) and 2 parts by mass of a copper phthalocyanine dye (CI Solvent Blue 70) are added and dissolved. Further, 250 parts by mass of water, 10 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier and 0.1 part by mass of sodium nitrite were added to this solution and mixed with strong stirring. Next, 66.6 parts by mass of the above dispersion (3) was added to this mixed solution, and the mixture was reacted at 50 to 78 ° C. for about 2 hours with stirring, and then aged at 90 ° C. for about 3 hours to obtain a polymer solid. As a result, a dispersion (8) of 31% by mass was obtained. That is, in a system in which such a polymerizable monomer (B) whose functional group is an amino group is interposed, a dye-encapsulated cyan colored particle in which a dye is held in and encapsulated in a formed particle as in the past. Prepared. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 3.9 μm. Next, this emulsion dispersion was filtered, dried and pulverized, and the charge amount of the obtained powder to iron was measured. As a result, it was 33 μC / g.

次いで、実施例５−２として、同様の容量１リットルの反応装置に、ＭＭＡ７８質量部を入れ、その他、実施例５−１において重合性モノマー（Ｂ）であるジエチルアミノメチルメタクリレートを投入させない以外は実施例５−１と同様にして、銅フタロシアニン系染料（Ｃ．Ｉ．ソルベントブルー７０）を形成粒子内に抱え込み内包させた染料内包型シアン着色粒子が固形分量は３０質量％の分散体（９）を調製した。この分散体を電子顕微鏡下に観察したところ、ほぼ一定の粒子径を有する単分散球状重合粒子で、その平均粒子径は３．８μｍであった。 Subsequently, Example 5-2 was carried out except that 78 parts by mass of MMA was put into a similar 1 liter reactor, and that diethylaminomethyl methacrylate which is a polymerizable monomer (B) in Example 5-1 was not added. In the same manner as in Example 5-1, a dispersion (9) in which a dye-encapsulated cyan colored particle in which a copper phthalocyanine-based dye (CI Solvent Blue 70) is encapsulated and encapsulated is 30% by mass Was prepared. When this dispersion was observed under an electron microscope, it was monodispersed spherical polymer particles having a substantially constant particle diameter, and the average particle diameter was 3.8 μm.

次いで、分散体（８）と分散体（９）の染料内包型シアン着色粒子のそれぞれを［水洗浄−脱水］の処理を３回繰り返し洗浄後の乾燥物（固形分は９９％以上）について色素色差計を用いて色評価を行いその結果を［表１］に示した。［表１］において、青色を表すｂ＊（ビースター）の値が本発明の重合性モノマー（Ｂ）としてアミノ基を導入した分散体（８）のシアン着色粒子粒子の方が、重合性モノマー（Ｂ）としてのアミノ基導入していない着色粒子よりマイナスに大きい。これはシアンの青色着色が濃いことを示している。以上から、粒子表面に局在するアミノ基により錯体染料の内包量が飛躍的に高まった。フタロシアニン系染料は分子量が大きく、嵩高い構造を有しているため通常のシード重合法では粒子内に内包され難いが、本発明のような重合性モノマー（Ｂ）を用いて重合反応持に、形成粒子内に染料を抱え込み内包させた染料内包型シアン着色粒子は、この粒子表面に頭出し状に局在する官能基による染料の吸引効果が高まり内包した染料を外に逃がさない構造を形成しているものと理解される。 Subsequently, each of the dye-encapsulated cyan colored particles of the dispersion (8) and the dispersion (9) is subjected to [water washing-dehydration] treatment three times, and the dried product (solid content is 99% or more) after washing. Color evaluation was performed using a color difference meter, and the results are shown in [Table 1]. In [Table 1], the cyan monomer particles of the dispersion (8) having an amino group introduced as the polymerizable monomer (B) of the present invention having a b * (beester) value representing blue is more polymerizable monomer. It is negatively larger than the colored particles to which no amino group is introduced as (B). This indicates that cyan blue coloring is deep. From the above, the inclusion amount of the complex dye was dramatically increased by the amino group localized on the particle surface. Since the phthalocyanine dye has a large molecular weight and a bulky structure, it is difficult to encapsulate the particles in a normal seed polymerization method. However, using the polymerizable monomer (B) as in the present invention, The dye-encapsulated cyan colored particles encapsulating and encapsulating the dye in the formed particles form a structure that increases the suction effect of the dye by the functional group localized in the head-like shape on the particle surface and does not let the encapsulated dye escape. It is understood that

（実施例６）
同様の容量２リットルの反応装置に、アセトンとイソプロピルアルコールとの２００質量部と、黒色染料のＣ．Ｉ．ＳｏｌｖｅｎｔＢｌａｃｋ２７の３０質量部と、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩の２５質量部と、２００質量部の水を加え強撹拌下に混合した。次いで、この混合溶液に実施例１で調製した分散体（４）（平均粒径４．１μｍ、固形分３０％）の５００質量部を添加し、５０℃で３０分間穏やかに撹拌処理後、９０℃で２時間の染色処理を行った。次いで、［脱水−水洗浄］を３回行った後の乾燥粉砕物は、平均粒子径４．１μｍの黒色球状粒子（１）であった。同様に、実施例５−２に準拠させて、染料を内包させないで、しかも、本発明における疎水性に富む重合性モノマー（Ｂ）であるジエチルアミノメチルメタクリレートを用いないで調製してアミノ基未含有粒子分散体（９）（４．２μｍ、固形分３１％）の２００質量部を同様にして染色処理をし、同様に洗浄・乾燥・粉砕して、平均粒子径４．２μｍの黒色球状微粒子（２）を調製し、それぞれ色素色差計を用いて色評価を行いその結果を［表２］に示した（なお、表中のＨＷが大きほど白い）。その結果、［表２］に示す白黒色の明度を示すＬ＊、白色度を示すＨＷの比較すると目視でも黒さの差が明らかであるが、黒色球状微粒子（１）の方が黒色球状微粒子（２）より黒いことを示している。 (Example 6)
In a similar 2-liter reactor, 200 parts by mass of acetone and isopropyl alcohol and C.I. I. 30 parts by mass of Solvent Black 27, 25 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier, and 200 parts by mass of water were added and mixed under strong stirring. Next, 500 parts by mass of the dispersion (4) prepared in Example 1 (average particle size 4.1 μm, solid content 30%) was added to the mixed solution, and after gently stirring at 50 ° C. for 30 minutes, 90 parts were obtained. The dyeing | staining process was performed at 2 degreeC for 2 hours. Next, the dried and pulverized product after performing [dehydration-washing with water] three times was black spherical particles (1) having an average particle size of 4.1 μm. Similarly, in accordance with Example 5-2, no dye is included, and it is prepared without using diethylaminomethyl methacrylate, which is a polymerizable monomer (B) rich in hydrophobicity in the present invention, and contains no amino group. 200 parts by mass of the particle dispersion (9) (4.2 μm, solid content 31%) were similarly dyed, washed, dried and ground in the same manner to obtain black spherical fine particles having an average particle diameter of 4.2 μm ( 2) were prepared, and color evaluation was performed using a dye color difference meter, respectively. The results are shown in [Table 2] (note that the larger HW in the table is whiter). As a result, when comparing L * indicating the brightness of the black and white color shown in [Table 2] and HW indicating the whiteness, a difference in blackness is apparent visually, but the black spherical fine particles (1) are more black spherical fine particles. (2) It shows that it is blacker.

（比較例１）
同様の容量１リットルの反応装置に、ＭＭＡ７８質量部、エチレングリコールジメタクリレート２質量部、その中にジメチル−２，２’−アゾビス（２−メチルプロピオネート）５質量部溶解させ、更にこの溶液に水２５０質量部、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部、亜硝酸ナトリウム０．１１質量部を加え強撹拌下に混合した。次いでこの混合溶液に分散体（３）の６６．６質量部を添加し、以下実施例２と同様にして、本発明における疎水性に富む重合性モノマー（Ｂ）であるβ−メタクリロイルオキシエチルハイドロジェンフタレートに代えて、メタクリル酸によるカルボキシル基を含有する球状重合体粒子分散体（１０）（平均粒径４．２μｍ、固形分３１％）を調製した。次いで、濾過・乾燥・粉化後、鉄に対する帯電量が、−１０μＣ／ｇ（表３に示す）であった。 (Comparative Example 1)
In a similar 1 liter reactor, 78 parts by mass of MMA, 2 parts by mass of ethylene glycol dimethacrylate, and 5 parts by mass of dimethyl-2,2′-azobis (2-methylpropionate) were dissolved therein. 250 parts by mass of water, 10 parts by mass of polyoxyethylene polycyclic phenyl ether sulfate as an emulsifier and 0.11 parts by mass of sodium nitrite were added and mixed under strong stirring. Next, 66.6 parts by mass of Dispersion (3) was added to this mixed solution, and β-methacryloyloxyethyl hydro hydride which is a polymerizable monomer (B) rich in hydrophobicity in the present invention, as in Example 2 below. A spherical polymer particle dispersion (10) (average particle diameter of 4.2 μm, solid content of 31%) containing a carboxyl group by methacrylic acid was prepared in place of genphthalate. Next, after filtration, drying, and pulverization, the charge amount with respect to iron was −10 μC / g (shown in Table 3).

（参考実験１）
同様の容量１リットルの反応装置に、ＭＭＡ７３質量部、エチレングリコールジメタクリレート２質量部、メタクリル酸５質量部を投入した。その中に過酸化ベンゾイル０．５質量部とジメチル−２，２’−アゾビス（２−メチルプロピオネート）１質量部を投入して溶解させ、更にこの溶液に水２５０質量部、乳化剤としてポリオキシエチレン多環フェニルエーテル硫酸エステル塩１０質量部および亜硝酸ナトリウム０．１質量部を加え強撹拌下に５分間混合した。次いでこの混合溶液に上記分散体（３）の６６．６質量部を添加し、５０℃で３０分間穏やかに撹拌した後、７８℃で１．５時間反応させ、その後９０℃で１．５時間熟成し、重合粒子の球状重合体粒子分散体（１１）（平均粒径４μｍ、固形分３１％）を調製した。 (Reference Experiment 1)
A similar 1 liter reactor was charged with 73 parts by mass of MMA, 2 parts by mass of ethylene glycol dimethacrylate, and 5 parts by mass of methacrylic acid. Into this solution, 0.5 part by mass of benzoyl peroxide and 1 part by mass of dimethyl-2,2′-azobis (2-methylpropionate) are added and dissolved. 10 parts by mass of oxyethylene polycyclic phenyl ether sulfate and 0.1 part by mass of sodium nitrite were added and mixed for 5 minutes under strong stirring. Next, 66.6 parts by mass of the dispersion (3) was added to this mixed solution, and after gently stirring at 50 ° C. for 30 minutes, the mixture was reacted at 78 ° C. for 1.5 hours, and then at 90 ° C. for 1.5 hours. After aging, a spherical polymer particle dispersion (11) of polymer particles (average particle size 4 μm, solid content 31%) was prepared.

官能基がカルボキシル基である重合性モノマー（Ｂ）を用いて実施例２で調製した機能性アクリル系ポリマー定形粒子の分散体（５）と、参考実験１で調製したメタクリル酸を添加したカルボキシル基含有架橋粒子の分散体（１１）とのそれぞれを洗浄・乾燥後、その酸価をそれぞれ測定した。そこで、溶媒としてトルエン／エタノール混合溶媒と、エタノール単独とを用いた。なお、前者のトルエン／エタノール（Ｔｏ／ＥｔＯＨ）の系では粒子の表面及び粒子内部に存在するカルボキシル基の酸価測定に用いられる（Ｔｏ／ＥｔＯＨ混合系溶媒は粒子への膨潤性、浸透性が富んでいるため粒子表面及び内部の酸化を測定することができる）。一方、後者の、エタノール単独での測定では粒子表面に存在するカルボキシル基の酸価測定に用いられる（ＥｔＯＨは粒子内部への膨潤、浸透性がＴｏ／ＥｔＯＨより低いため粒子のより表面の酸化を測定することができる）。 Dispersion (5) of functional acrylic polymer shaped particles prepared in Example 2 using a polymerizable monomer (B) whose functional group is a carboxyl group, and a carboxyl group added with methacrylic acid prepared in Reference Experiment 1 After washing and drying each of the containing crosslinked particle dispersion (11), the acid value thereof was measured. Therefore, a toluene / ethanol mixed solvent and ethanol alone were used as the solvent. In the former toluene / ethanol (To / EtOH) system, it is used to measure the acid value of the carboxyl group present on the surface of the particle and inside the particle (the To / EtOH mixed system solvent has the ability to swell and penetrate into the particle. Because it is abundant, it is possible to measure the oxidation of the particle surface and inside). On the other hand, the latter measurement with ethanol alone is used to measure the acid value of the carboxyl group present on the particle surface (EtOH swells inside the particle, and its permeability is lower than To / EtOH, so the surface of the particle is more oxidized). Can be measured).

以上から、［表４］に示す酸価の測定値から明らかなように、分散体（５）すなわち、本発明の官能基が重合性モノマー（Ｂ）由来のアクリル系粒子では、測定溶剤のＴｏ／ＥｔＯＨ混合系及びＥｔＯＨ単独系とも、実測値に変化がなくほぼ理論値であることから、官能基カルボキシル基の殆どが粒子表面に存在（局在）していることを示すものである。一方、分散体（１１）すなわち、官能基の多くが粒子内に内包すると思われる従来のカルボキシル基含有粒子は、Ｔｏ／ＥｔＯＨ混合系の測定酸価値が、ほぼ理論値に等しく、しかも、ＥｔＯＨ単独系では理論値の約１／３であることから、カルボキシル基が粒子表面だけではなく、その大部分が粒子内部に存在していると思われる。 From the above, as is apparent from the measured acid values shown in [Table 4], in the dispersion (5), that is, in the acrylic particles in which the functional group of the present invention is derived from the polymerizable monomer (B), To of the measurement solvent is used. In both the / EtOH mixed system and the EtOH single system, there is no change in the actual measurement value and it is almost the theoretical value, which indicates that most of the functional group carboxyl groups are present (localized) on the particle surface. On the other hand, in the dispersion (11), that is, in the conventional carboxyl group-containing particles that many functional groups are supposed to be included in the particles, the measured acid value of the To / EtOH mixed system is almost equal to the theoretical value, and EtOH alone In the system, since it is about 1/3 of the theoretical value, it seems that most of the carboxyl groups are present not only on the particle surface but also inside the particle.

（参考実験２）
カルボキシル基含有粒子の分散体（５）（固形分濃度３３％）と官能基未含有粒子の分散体（１１）のそれぞれをイソプロパノール中に再分散させ、それぞれシランカップリング剤Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシランを１０質量部添加し、９０℃で５時間還流しながら反応させた。得られたそれぞれの粒子を（５−１）及び（１１−１）として、反応前・後の粒子を濾過・洗浄・乾燥し、ＩＲ測定を行った。 (Reference Experiment 2)
Each of the carboxyl group-containing particle dispersion (5) (solid content concentration 33%) and the functional group-free particle dispersion (11) was redispersed in isopropanol, and the silane coupling agent N-2 (aminoethyl), respectively. ) 10 parts by mass of 3-aminopropyltrimethoxysilane was added and reacted at 90 ° C. while refluxing for 5 hours. Using the obtained particles as (5-1) and (11-1), the particles before and after the reaction were filtered, washed and dried, and IR measurement was performed.

その結果、粒子（５）、（５−１）及び（１１−１）のＩＲを比較すると、反応後の（５−１）には１６３０ｃｍ−^１に一級アミン、７５０ｃｍ−^１に第２級アミンのそれぞれの吸収スペクトルが確認され、粒子（５）及び（１１−１）には全く確認されなかった。このことから、粒子表面上に存在するカルボキシル基とシランカップリング剤であるＮ−２（アミノエチル）３−アミノプロピルトリメトキシシランが反応し、粒子表面に官能基が存在している証であると考えられる。 As a result, particles (5), (5-1) and (11-1) When comparing the IR, the following reaction (5-1) primary amine in 1630Cm- ^1, secondary amine to 750Cm- ¹ The respective absorption spectra were confirmed, and were not confirmed at all in the particles (5) and (11-1). From this, it is proof that the carboxyl group existing on the particle surface reacts with N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, which is a silane coupling agent, and the functional group exists on the particle surface. it is conceivable that.

以上から、本発明によれば、（メタ）アクリル系モノマー（Ａ）と、特に官能基に係わって特定の分子構造を有する疎水性の重合性モノマー（Ｂ）とを共重合させてなる構造的な構成要件に起因させて、官能基が重合体定形粒子の表面に頭出し状に局在し、しかも、特定量の官能基量が明確に形成されていることを特徴とする機能性アクリル系ポリマー定形粒子である。 As described above, according to the present invention, the structural unit obtained by copolymerizing the (meth) acrylic monomer (A) and the hydrophobic polymerizable monomer (B) having a specific molecular structure particularly related to the functional group. The functional acrylic is characterized in that the functional group is localized in the form of a cue on the surface of the polymer regular particle, and the specific amount of the functional group is clearly formed. Polymer shaped particles.

そこで、このような本発明による機能性アクリル系ポリマー定形粒子は、その官能基種によって、適宜（＋）帯電又は（−）帯電性粒子として調製され、その帯電性をブローオフ法による絶対値で表す表面帯電量Ｃ（μＣ／ｇ）で表す数値として、１０≦｜Ｃ｜≦５００の範囲にある帯電性ポリマー定形粒子を提供することができる。 Therefore, such functional acrylic polymer regular particles according to the present invention are appropriately prepared as (+) charged or (−) charged particles depending on the functional group type, and the chargeability is expressed as an absolute value by a blow-off method. As a numerical value represented by the surface charge amount C (μC / g), a chargeable polymer regular particle in a range of 10 ≦ | C | ≦ 500 can be provided.

また、粒子表面に多く頭出し状に局在する例えば、−ＣＯＯＨ、−ＮＨ_３、−ＯＨ等の官能基を介して、イオン交換法で各種の金属元素及び遷移金属元素の金属イオンを担持させられることから、数百ｎｍ〜数十μｍなる広範なサイズに及ぶイオン交換定形粒子として、また、その表面の特定量の官能基に係わって、しかも、イオン交換性及び化学的活性等が生かされたクロマトカラム充填剤として提供することができる。 Also, metal ions of various metal elements and transition metal elements are supported by an ion exchange method through functional groups such as —COOH, —NH ₃ , —OH, etc. As a result, the ion-exchange shaped particles having a wide range of several hundred nm to several tens of μm, and related to a specific amount of functional groups on the surface, the ion exchange property and chemical activity are utilized. It can be provided as a chromatography column packing material.

また、このようなに官能基が粒子表面に多く頭出し状に局在しているアクリル系ポリマー定形粒子を用いれば、従来のように重合反応時に、形成粒子内に染料を抱え込み内包させる染料内包型着色ではなく、通常の染色法で、有彩色に又は無彩色の黒色に粒子表面の近傍相を含む粒子表面を効果的に染色させられる。このように染色着色された球状着色粒子は、ファクシミリ、複写機、レーザプリンター等の電子写真画像形成用の静電トナー定形粒子として提供することができる。 In addition, if acrylic polymer regular particles having many functional groups localized on the surface of the particle are used as described above, the dye inclusion that encloses the dye in the formed particle and encapsulates it during the polymerization reaction as in the past. It is possible to effectively dye the particle surface including the phase near the particle surface in chromatic color or achromatic black color by an ordinary dyeing method instead of mold coloring. The spherical colored particles thus dyed and colored can be provided as electrostatic toner regular particles for forming an electrophotographic image such as a facsimile, a copying machine, and a laser printer.

また、本発明による機能性アクリル系ポリマー定形粒子としての染色法で有彩色に又は無彩色の黒色に染色着色された球状粒子をボールペンインク、ＩＪプリンター用インク、印刷用水性インク、筆記用水性インク及びスタンプ用インクや、その他の感温色材、コーティング剤、水性塗料及びカラー化粧料等のカラー着色料に、また、特に黒色に染色着色された球状粒子は画像表示装置に用いられる遮光性粒子に、また、特に、染色法で黒色系無彩色に染色着色された電子顕微鏡法で表す平均粒子径が１００〜５００ｎｍの単分散の球状粒子な構造色形成用の黒色系無彩色球状粒子として提供することができる。 Further, spherical particles dyed and colored in chromatic or achromatic black by the dyeing method as the functional acrylic polymer regular particles according to the present invention are used for ballpoint pen ink, ink for IJ printer, aqueous ink for printing, aqueous ink for writing. In addition, spherical particles that are dyed and colored in black, such as ink for stamping, other temperature-sensitive color materials, coating agents, water-based paints, color cosmetics, and the like, are used in image display devices. Also provided in particular as black achromatic spherical particles for the formation of monodispersed spherical particles having an average particle diameter of 100 to 500 nm expressed by electron microscopy, which are dyed and colored in black achromatic colors by a staining method. can do.

また、更には、このような本発明による帯電性・着色球状粒子は、上述する電子写真画像装置の電界系で用いられ所望する帯電性の静電着色トナーの他に、所望する高帯電・電気泳動性を発揮させてＰＬＤ用の画像表示及び／又は印字表示のディスプレイ粒子として提供することができる。
Further, such chargeable / colored spherical particles according to the present invention are used in the electric field system of the electrophotographic image apparatus described above, and in addition to the desired electrostatic chargeable toner, the desired highly charged / electrically charged particles. It can be provided as display particles for image display and / or print display for PLD by exhibiting electrophoretic properties.

Claims

In functional acrylic polymer regular particles with functional groups localized on the particle surface,
1-100 parts by mass of the polymerizable monomer (B) having at least one functional group in the molecule and rich in hydrophobicity per 100 parts by mass of the (meth) acrylic monomer (A). A copolymer obtained by polymerization in a range, and expressed in terms of mass%, is localized so that at least 70% or more of the total amount of the functional groups in the shaped particles starts at the surface of the shaped particles. Functional acrylic polymer shaped particles characterized by

The polymerizable monomer (B) has a polymerizable group, any one functional group selected from a carboxyl group, a hydroxyl group, and an amino group, and a hydrophobic group having 4 or more carbon atoms. The functional acrylic polymer shaped particle according to claim 1.

The polymerizable monomer (B) is represented by the following formulas (1) to (3):

Or

The functional acrylic polymer regular particle according to claim 2, which is any one hydrophobic monomer having the structure:

The particle shape of the regular particles is a monodisperse particle having a true spherical shape or an elliptical spherical shape, and an average particle diameter represented by a number average is in a range of 20 nm to 50 µm. Functional acrylic polymer shaped particles.

The functional acrylic polymer regular particles according to any one of claims 1 to 4, wherein the numerical value of the surface charge amount C (μ · coulomb / g) expressed by an absolute value by a blow-off method is in a range of 10 ≦ | C | ≦ 500. Chargeable polymer shaped particles characterized in that

Using any of the functional acrylic polymer regular particles according to any one of claims 1 to 4, it is selected from metal elements and transition metal elements belonging to Groups 1 to 15 of the Periodic Table of Elements by an ion exchange method. A metal ion-supported polymer shaped particle, wherein at least one metal ion is supported.

A fixed form for electrophotographic image formation, characterized in that the functional acrylic polymer regular particle according to any one of claims 1 to 4 is dyed chromatic or achromatic black by a dyeing method. Color toner.

Colored spherical particles for ball-point pen ink, characterized in that the functional acrylic polymer regular particles according to any one of claims 1 to 4 are dyed in a chromatic or achromatic black color by a dyeing method. .

A light-shielding spherical particle for an image display device, wherein the functional acrylic polymer regular particle according to any one of claims 1 to 4 is dyed black by a dyeing method.

The monodispersed spherical particles according to claim 4, which are dyed in black achromatic color by a dyeing method using functional acrylic polymer regular particles having an average particle diameter in the range of 100 to 500 nm expressed by electron microscopy. Achromatic black spherical particles for forming a structural color.

A color cosmetic comprising the functional acrylic polymer regular particle according to any one of claims 1 to 4, which is dyed in a chromatic color by a dyeing method.

The spherical polymer regular particle according to any one of claims 1 to 4, wherein the functional acrylic polymer regular particle having a predetermined amount of functional groups localized on the particle surface is used. filler.